EP3283540A1 - Dispersions aqueuses de polyuréthane - polyacrylate - Google Patents

Dispersions aqueuses de polyuréthane - polyacrylate

Info

Publication number
EP3283540A1
EP3283540A1 EP16719267.3A EP16719267A EP3283540A1 EP 3283540 A1 EP3283540 A1 EP 3283540A1 EP 16719267 A EP16719267 A EP 16719267A EP 3283540 A1 EP3283540 A1 EP 3283540A1
Authority
EP
European Patent Office
Prior art keywords
component
polyurethane
polyacrylate dispersion
aqueous polyurethane
aliphatic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP16719267.3A
Other languages
German (de)
English (en)
Inventor
Pantea Nazaran
Rolf Gertzmann
Tanja Hebestreit
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Covestro Deutschland AG
Original Assignee
Covestro Deutschland AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Covestro Deutschland AG filed Critical Covestro Deutschland AG
Publication of EP3283540A1 publication Critical patent/EP3283540A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C08G18/348—Hydroxycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44—Polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
    • C08G18/722—Combination of two or more aliphatic and/or cycloaliphatic polyisocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/06—Polyurethanes from polyesters

Definitions

  • the invention relates to an aqueous polyurethane-polyacrylate dispersion and a process for its preparation. Further objects of the invention are a coating composition containing the aqueous polyurethane-polyacrylate dispersion, and the use of this coating agent for producing a coating. Moreover, the invention relates to a composite of the coating and a substrate.
  • Aqueous polyurethane dispersions are suitable for the production of a variety of coatings and are characterized by very good properties, such as. Abrasion resistance, flexibility or toughness.
  • polyurethane-polymer hybrid dispersions such as polyurethane-polyacrylate dispersions are known.
  • Polyacrylate dispersions often have increased hardness and resistance to chemicals and weathering.
  • a combination of polyurethane and polyacrylate dispersions may even provide synergistic effects.
  • the above-mentioned hybrid dispersions can be chemically and / or physically linked to one another. In this physical link, one can also speak of a physical blend.
  • WO 2011/089154 A1 discloses a process for the preparation of aqueous polyurethane-polyacrylate dispersions in which the polyurethane contains ethylenically unsaturated groups which are reacted with ethylenically unsaturated monomers. Via the crosslinking reaction of the unsaturated groups, chemically linked polymers are obtained.
  • Polyurethane-polyacrylate hybrid systems in which the polyurethane and the polyacrylate do not chemically bond with each other but interact only physically, are disclosed for example in EP 1124871 Bl.
  • the described polyurefhan-polyacrylate hybrid dispersion is prepared by a pre-emulsified mixture of monomer and lipophilic (oil-soluble) initiator in the presence of a polyurethane.
  • the radical polymerization takes place in this method in the monomer droplets.
  • this method of preparation is not suitable, for example when very hydrophobic acrylate monomers which are not sufficiently soluble in water are used, or when the monomer mixture and / or initiator solution are to be dosed to produce certain polymer morphologies, e.g. To achieve hybrid dispersions with a core-shell morphology of the polymer particles.
  • the dispersions prepared by the method described in EP 1124871 Bl have insufficient stability or can not be prepared at all due to the use of a lipophilic initiator in the absence of an additional emulsifier.
  • aqueous polyurethane dispersions described at the outset are already used, for example, for coatings in the automotive sector. By avoiding organic solvents even stricter environmental regulations can be met. To make the painting process more efficient, for example, less paint layers can be applied or the thickness of the paint layers can be reduced.
  • aqueous polyurethane-polyacrylate dispersion which would become binders having improved stability to shear forces over the polyurethane-polyacrylate known in the art. Dispersions leads and from which also coatings with a very good opacity, hardness, chemical and weather resistance and a good flip-flop effect can be produced.
  • a further object of the present invention was to provide a solvent-free and emulsifier-free aqueous polyurethane-polyacrylate dispersion having the same properties as described above.
  • an aqueous polyurethane-polyacrylate dispersion obtainable by free-radical polymerization of a component A) comprising an ethylenically unsaturated compound, at least in the presence of a component B) comprising water and a polyurethane resin obtainable by reacting the following structural components I) comprising at least one aliphatic, cycloaliphatic, araliphatic and / or aromatic compound having at least two or more isocyanate groups,
  • V comprising at least one or more monoalcohols and / or monoamines, wherein a hydrophilic initiator is used as initiator of the radical polymerization, dissolved.
  • hydrophilic initiator is understood as meaning a chemical compound which has a high affinity for water or a high tendency to solvate in water and acts as a radical initiator.
  • the stability to shear forces of the polyurethane-polyacrylate dispersions according to the invention is also referred to as ring-line stability.
  • the loop stability can be simulated, for example, by means of a Göttfert capillary rheometer, as in K. Georgieva, DJ. Dijkstra, H. Fricke, N. Willenbacher, /. Colloid Interface Be. 2010, 352, 265-277.
  • Figure 1 and Table 1 on page 267 of K. Georgieva et al. are shown the apparatus and technical specifications used for the present application.
  • the binder to be examined is placed in the container provided for this purpose and by means of a movable cylinder at a constant speed an annular gap of 20 ⁇ gap size pressed.
  • the greater the shear stability of the binder the smaller the pressure build-up when pressing through the annular gap.
  • the simulated shear forces can be calculated from the gap size and the speed.
  • the mass ratio of the components A) and B) can be freely selected over a wide range.
  • the component A) in 3 to 40 wt .-%, preferably in 5 to 30 wt .-% and particularly preferably in 7 to 25 wt .-%, the component B) in 97 to 60 wt. %, preferably in 95 to 70 wt .-% and particularly preferably in 93 to 75 wt .-%, based on the total amount of the polyurethane-polyacrylate dispersion, used wherein the proportions are normalized so that they also with optional use of additional Components C) can not be greater than 100% and particularly preferably complement each other to 100%.
  • the initiation of the polymerization takes place with the customary for free radical polymerization hydrophilic initiators.
  • These include water-soluble inorganic persulfates, such as ammonium or sodium persulfate.
  • the hydrophilic initiator comprises one or more persulfate-containing compounds, is preferably exclusively one or more persulfate-containing compounds and is particularly preferably exclusively ammonium peroxodisulfate, sodium peroxodisulfate and / or potassium peroxodisulfate.
  • component A) comprises at least one aliphatic, cycloaliphatic or aromatic acrylate or methacrylate which is substituted or unsubstituted, preferably at least one aliphatic or cycloaliphatic, optionally alkyl-substituted acrylate or methacrylate and particularly preferably at least one mixture of an aliphatic, optionally alkyl substituted acrylate and an aliphatic, optionally alkyl substituted methacrylate.
  • Suitable ethylenically unsaturated compounds for component A) are one or more of the following compounds:
  • Vinylaromatic compounds VI in particular having up to 20 carbon atoms, are, for example, styrene, vinyltoluene, o- and p-methylstyrene, butylstyrene, decylstyrene, halogenated styrenes, for example monochlorostyrenes, dichlorostyrenes, tribromostyrenes or tetrabromostyrenes. Preference is given to styrene.
  • Suitable acrylic esters VII) include, in particular, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, sec-butyl acrylate, tert-butyl acrylate, pentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, 2-octyl acrylate, ethylhexyl acrylate, nonyl acrylate, 2-methyl octyl acrylate, 2- (tert-butyl) heptyl acrylate, 3- (iso-propyl) heptyl acrylate, decyl acrylate, undecyl acrylate, 5-methylundecyl acrylate, dodecyl acrylate, 2-methyldodecyl acrylate, tridecyl acrylate, 5-methyltridecyl acrylate
  • ethyl acrylate Preference is given to ethyl acrylate, n-butyl acrylate, ethylhexyl acrylate, cyclohexyl acrylate, particular preference to ethylhexyl acrylate.
  • Suitable polyvinylidene compounds VIII include those compounds which have at least two olefinically unsaturated bonds. These include, in particular, acrylic or methacrylic acid esters of polyols of functionality> 2, e.g. Ethylene glycol diacrylate, diethylene glycol diacrylate, glycerol diacrylate, glycerol triacrylate, ethylene glycol dimethacrylate, 1,3-propanediol diacrylate, 1,3-propanediol dimethacrylate, 1,4-butanediol diacrylate, 1,4-
  • acrylic or methacrylic acid esters of polyols of functionality> 2 e.g. Ethylene glycol diacrylate, diethylene glycol diacrylate, glycerol diacrylate, glycerol triacrylate, ethylene glycol dimethacrylate, 1,3-propanediol diacrylate, 1,3-propanediol dimethacrylate, 1,4
  • 1,4-butanediol diacrylate trimethylolpropane dimethacrylate, ethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, particularly preferably ethylene glycol dimethacrylate or 1,6-hexanediol dimethacrylate.
  • Suitable esters IX) of methacrylic acid include in particular methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, sec- Butylmethacrylate, tert-butylmethacrylate, pentylmethacrylate, hexylmethacrylate, heptylmethacrylate, octylmethacrylate, 2-octylmethacrylate, ethylhexylmethacrylate, nonylmethacrylate, 2-methyloctylmethacrylate, 2- (tert-butyl) heptylmethacrylate, 3- (iso-propyl) heptylmethacrylate, decylmethacrylate, undecylmethacrylate, 5- Methylundecylmethacrylat, dodecyl methacrylate, 2- Methy
  • the methacrylic acid derivatives can also be used in the form of the corresponding nitriles or amides, such as methacrylonitrile or methacrylamide.
  • other functional monomers such as diacetone methacrylamide or acetoacetoxyethyl methacrylate.
  • Preferred are methyl methacrylate, ethyl methacrylate, butyl methacrylate, tert-butyl methacrylate, particularly preferred are methyl methacrylate, tert-butyl methacrylate or butyl methacrylate.
  • Construction component I) Suitable aliphatic, cycloaliphatic, araliphatic and / or aromatic compounds having at least two or more isocyanate groups are, for example, di- or triisocyanates of the molecular weight range 140 to 400.
  • Preferred diisocyanates are 1,4-diisocyanatobutane, 1,5-diisocyanatopentane (PDF), 1,6-diisocyanatohexane (HDI), 1,5-diisocyanato-2,2-dimethylpentane, 2,2,4- and 2,4 respectively , 4-trimethyl-l, 6-diisocyanatohexane, 1,10-diisocyanatodecane, 1,3- and 1,4-diisocyanatocyclohexane, 1,4-diisocyanato-3,3,5-trimethylcyclohexane, 1,3-diisocyanato-2-one methylcyclohexane, 1,3-diisocyanato-4-methylcyclohexane, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), 1-isocyanato-1
  • the synthesis component I) comprises at least one aliphatic, cycloaliphatic, aliphatic and / or aromatic diisocyanate, preferably a mixture of aliphatic and / or cycloahphatic diisocyanates and particularly preferably a mixture of 1,6-diisocyanatohexane, 1-isocyanate 3,3,5-trimethyl-5-isocyanatomethylcyclohexane and / or 4,4'-diisocyanato-dicyclohexylmethane.
  • the preparation of the above diisocyanates can be prepared by known methods, for. B. by phosgenation or phosgene-free way, for example, by urethane cleavage done. It is also possible to use proportionately up to 5% by weight, based on the polyurethane solid resin, of trihydric and / or higher isocyanates, in order thus to ensure a certain degree of branching or crosslinking of the polyurethane.
  • Such isocyanates are e.g. are obtained by reacting divalent isocyanates with each other such that a part of their isocyanate groups are derivatized to isocyanurate, biuret, allophanate, uretdione or carbodiimide groups. Such polyisocyanates hydrophilized via ionic groups are also suitable. Such polyisocyanates may have high functionality, e.g. of more than 3.
  • the synthesis component II) comprises at least one polycarbonate polyol having an average molecular weight of 500 to 3000 g / mol.
  • the polycarbonate polyol has an average molecular weight of from 1000 to 3000 g / mol, preferably from 1250 to 2500 g / mol and more preferably from 1500 to 2100 g / mol.
  • the average molecular weight of the polycarbonate polyol can be determined by GPC (gel permeation chromatography) according to DIN 55672-1.
  • the selected polycarbonate polyols can have an OH functionality of from 1.8 to 5, preferably from 1.9 to 3 and particularly preferably from 1.9 to 2.0, and can be prepared by known processes.
  • Suitable polycarbonates are obtainable, for example, by reacting diphenyl carbonate, dimethyl carbonate or phosgene with polyols, preferably diols.
  • suitable diols are ethylene glycol, 1,2- and 1,3-propanediol, 1,3- and 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, neopentyl glycol, 1,4-bis-hydroxymethyl-cyclohexane , 2-methyl-l, 3-propanediol, 2,2,4-trimethylpentane-1,3-diol, dipropylene glycol, polypropylene glycol, dibutylene glycol, polybutylene glycol, bisphenol A, tetrabromobisphenol A but also lactone-modified diols can be used.
  • the diol 40 to 100 wt .-% of hexanediol, preferably 1,6-hexanediol and / or hexanediol derivatives, particularly preferably those which in addition to terminal OH groups ether or ester groups, for example products which by reacting 1 mol of 1,6-hexanediol with at least 1 mole, preferably 1 to 2 moles of caprolactone or by Etherification of 1,6-hexanediol with itself to di- or Trihexylenglykol were obtained contains.
  • the polyether-polycarbonate diols described in DE-A 37 17 060 can also be used.
  • the polycarbonate polyols are linear. However, they may optionally be easily branched by the incorporation of polyfunctional components, especially low molecular weight polyols.
  • polyfunctional components especially low molecular weight polyols.
  • glycerol, trimethylolpropane, hexanetriol-1,2,6, butanetriol-1,2,4, trimethylolethane, pentaerythritol, quinitol, mannitol and sorbitol, methyl glycoside or 1,3,3,6-dianhydrohexitols are suitable for this purpose.
  • polyester In addition to the polycarbonate polyols essential to the invention, it is also possible to use e.g. Polyester, polyethers, polyacetals, polyolefins, polyacrylates and polysiloxanes are used. Polyester and / or polyethers are preferably used as further polyol component.
  • Component B) preferably contains the further polyol component at less than 10% by weight, or preferably at less than 5% by weight, or preferably at less than 3% by weight, or preferably at less than 1% by weight. , or preferably in a range of 0.001 to 10 wt .-%, or preferably in a range of 0.001 to 5 wt .-%, or preferably in a range of 0.002 to 3 wt .-%, or preferably in a range of 0.003 to 1 wt .-%, each based on the total amount of component B).
  • Component B) preferably contains polyester polyol and / or polyether polyol as further polyol component to less than 10% by weight, or preferably to less than 5% by weight, or preferably to less than 3% by weight, or preferably to less than 1 wt%, or preferably in a range of 0 to 10 wt%, or preferably in a range of 0.001 to 5 wt%, or preferably in a range of 0.002 to 3 wt%, or preferably in a range of 0.003 to 1 wt .-%, each based on the total amount of component B).
  • the structural component I) preferably contains no polyether polyol and / or polyester polyol.
  • component B) has no polyether polyol and / or polyester polyol.
  • the synthesis component III) comprises at least one anionically hydrophilicizing compound which has at least one OH or NH-functional group and contains a carboxyl and / or carboxylate group.
  • the anionically hydrophilizing compound is free of sulfonic acid groups and sulfonate groups, preferably comprises dimethylolpropionic acid, dimethylolpropionate, N- (2-aminoethyl) -2-aminoethane carboxylic acid and / or N- (2-aminoethyl) -2-aminoethanoate and particularly preferably consists of dimethylolpropionic acid, dimethylolpropionate, N- (2-aminoethyl) -2-aminoethanecarboxylic acid and / or N- (2-aminoethyl) -2-aminoethanoate.
  • the structural component IV) comprises at least one polyol and / or polyamine having an average molecular weight between> 62 and ⁇ 500 g / mol, preferably between> 62 to ⁇ 400 g / mol and more preferably between> 90 to ⁇ 300 g / mol.
  • ethanediol 1,2- and 1,3-propanediol, 1,2-, 1,3- and 1,4-butanediol, 1,5-pentanediol, 3-methyl-pentanediol-1, 5, 1,6-hexanediol, neopentyl glycol, cyclohexane-1,4-dimethanol, 1,2- and 1,4-cyclohexanediol, 2-ethyl-3-propyl-pentanediol, 2,4-dimethyl-pentanediol, 2-ethyl-2 Butylpropandiol, diethylenetriamine, ethylenediamine, ether oxygen-containing diols, such as Diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, polyethylene, polypropylene or polybutylene glycols, N-sub
  • Preferred polyols are 1,4-butanediol, 1,5-pentanediol, 3-methylpentanediol-1,5, 1,6-hexanediol, neopentyl glycol, cyclohexane-1,4-dimethanol, 1,2- and 1,4- Cyclohexanediol and N-substituted ethanolamines.
  • Very particularly preferred polyols and / or polyamines are 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, diethylenetriamine, ethylenediamine, and N-substituted ethanolamines.
  • Tri- and higher-functional alcohols of the stated molecular weight range can be used proportionally in an amount, so that the polymer solution remains stirrable.
  • Such components include, for example, trimethylolpropane, glycerol, and pentaerythritol.
  • the optional component V) comprises at least one or more monoalcohols and / or monoamines.
  • these compounds can have 1 to 18 C atoms.
  • Suitable monoalcohols or monoamines are, for example, ethanol, 1-propanol, 2-
  • ethanol Preference is given to ethanol, n-butanol, ethylene glycol monobutyl ether, 2-ethylhexanol, 1-octanol, 1-dodecanol, 1-hexadecanol, butylamine, propylamine, aminoethanol, dimethylethanolamine, Aminopropanol, diethanolamine or dibutylamine used.
  • Particularly preferred are n-butanol and ethylene glycol monobutyl ether.
  • Component B) comprises a polyurethane resin and water.
  • the polyurethane resin is obtainable by a process in which the synthesis components II), III), IV) and optionally V) are separated and reacted in any order or as a mixture with the synthesis component I) and the synthesis component III) before, during or after Transfer of the polyurethane resin, which is preferably present at 99 to 65 wt .-%, more preferably 95 to 70 wt .-%, most preferably 90 to 80 wt .-% dissolved in a suitable solvent, neutralized and the polyurethane resin is dispersed in water , Ideally, the synthesis component V) is added only if the reactivity toward isocyanate groups is moderate and thus does not lead to gelling of the batch. In this case, both the synthesis component I) and one or more of the components II) -V) can be submitted. Preference is given to component I), the components II) -V) are metered in and reacted with component I).
  • the component B) after the reaction of the structural components I) to V) no aliphatic C-C double bonds.
  • the synthesis components I) to V) can be used to prepare the polyurethane resin in any proportions. However, it is hereby preferred that the synthesis components I) to V) in proportions of
  • the polyurethane resin are used and the proportions are chosen so that they can not be greater than 100%, and particularly preferably to 100% complement.
  • Suitable solvents For example, acetone, methyl ethyl ketone, tetrahydrofuran and tert-butyl methyl ether, acetone is preferred.
  • solvent-free in the sense of the present application means that maximum solvent amounts of ⁇ 0.9 wt .-%, preferably ⁇ 0.5 wt .-%, more preferably ⁇ 0.3 wt .-% may remain in the dispersion.
  • Suitable neutralizing agents are alkaline organic and / or alkaline inorganic compounds. Preferred are, in addition to aqueous ammonia, ethylamine and dimethylamine solutions, volatile primary, secondary and tertiary amines, e.g. Dimethylethanolamine, morpholine, N-methylmorpholine, piperidine, diethanolamine, triethanolamine, diisopropylamine, 2-amino-2-methylpropanol and 2-N, N-dimethylamino-2-methylpropanol or mixtures of these compounds. Particularly preferred are unreactive towards isocyanates tertiary amines such. Triethylamine, diisopropylethylamine and N-methylmorpholine and mixtures of these tertiary amines, which are preferably added to the prepolymer prior to dispersion.
  • volatile primary, secondary and tertiary amines e.g. Dimethylethanolamine, morpholine, N-methylmorpho
  • the dispersion can be adjusted very finely divided, so that it has practically the appearance of a solution.
  • the solids content of the dispersion obtained after distillation of the solvent can be varied within wide limits, for example from 20 to 65 wt .-%.
  • a preferred solids range here ranges from 30 to 50% by weight and particularly preferred is a solids content of 33 to 45% by weight.
  • component B may contain additional water.
  • the polyurethane-polyacrylate dispersion according to the invention may also contain an optional component C).
  • the optional component C) may comprise, for example, further polymers such as polyacrylate dispersions or polyurethane dispersions.
  • the polyurethane-polyacrylate dispersion has no further component C) in addition to the components A) and B).
  • the following structural components exist I), of at least one aliphatic, cycloaliphatic, aliphatic and / or aromatic compound having at least two or more isocyanate groups,
  • component B) comprises a polyester polyol and / or a polyether polyol as further polyol component together to less than 10 wt .-%, preferably less than 5 wt .-%, or preferably less as 3 wt .-%, based on the total weight of component B).
  • a process for the preparation of the aqueous polyurethane-polyacrylate dispersion according to the invention is a further subject of the present invention.
  • the radical polymerization of component A) is carried out in the presence of at least the hydrophilic initiator and component B).
  • component B) is initially charged and the free-radical polymerization is metered in by metering component A) in the presence of at least the hydrophilic initiator, which preferably also continuously in parallel with the metered addition of component A) to the component B) introduced will be performed.
  • the metered addition may be carried out batchwise or continuously, preference being given here to continuous metered addition.
  • the continuous metering can be carried out over any period, which is selectable depending on the quantities to be used.
  • the choice of the appropriate period can also be used specifically to control the morphology of the polyurethane-polyacrylate dispersion according to the invention, since the forming polyacrylate oligomers are oriented in the polyurethane particles and thus the structure of the core-shell morphology can be influenced.
  • further solvent preferably water
  • further solvent preferably water
  • the hydrophilic initiator is likewise metered in continuously to component B) in parallel with the continuous metered addition of component A) to component B).
  • the hydrophilic initiator may be added dissolved in bulk or in a suitable solvent. In this case, it is preferred if the initiator is metered in dissolved in a solvent. Very particular preference is given to using water as the solvent.
  • the initiator concentration can be freely selected over a wide range, but the concentration of the hydrophilic initiator in the selected solvent is preferably in a range of> 0.001 to ⁇ 5 wt .-%, preferably from> 0.01 to ⁇ 3 wt. -% and particularly preferably from> 0.1 to ⁇ 2 wt .-%.
  • component A) can be added in its total amount to be used in one step or in several portions.
  • a portion of component A) is added in parallel with a portion of the optionally dissolved, hydrophilic initiator in a first step to the component B) and the resulting mixture then up to 5 hours, preferably until is stirred for 3 hours and more preferably up to one hour, before the remaining component A) is added in parallel with the remaining, optionally dissolved, hydrophilic initiator to the stirred mixture.
  • the addition within the portions is preferably carried out continuously.
  • the mixture obtained can be stirred for a certain time, preferably up to 5 hours and more preferably up to 3 hours.
  • the radical polymerization of component A) in the presence of at least the hydrophilic initiator and component B) may preferably be carried out at temperatures between> 30 ° C and ⁇ 95 ° C. It is irrelevant whether component B) is heated before or during the addition of component A) and the initiator. However, it is particularly preferred if the temperature is between> 40 ° C and ⁇ 90 ° C. This results in the advantage that the reaction rate can be increased without the risk of destabilization of the polyurethane dispersion.
  • the free radical polymerization of component A) takes place in the presence of a hydrophilic initiator and component B) in the absence of additional emulsifiers.
  • the resulting polyurethane-polyacrylate dispersion of the invention can also be filtered.
  • the polyurefan polyacrylate dispersion according to the invention has a solids content of from 20 to 70% by weight, preferably from 30 to 60% by weight and particularly preferably from 40 to 50% by weight.
  • the polyurethane-polyacrylate dispersion according to the invention is particularly preferably solvent-free in the sense of the present invention.
  • aqueous polyurethane-polyacrylate dispersion according to the invention is suitable for a large number of applications, for example as a binder component in a coating composition. Due to the very low proportion of solvents which may be present, other than water, the dispersion according to the invention has particularly advantageous environmental properties.
  • compositions comprising at least one inventive polyurethane-polyacrylate dispersion and at least one crosslinking agent and optionally further auxiliaries and additives.
  • crosslinking agents are amide and amine-formaldehyde resins, phenol resins, aldehyde and ketone resins, for example phenol-formaldehyde resins, resols, furan resins, urea resins, carbamic acid ester resins, triazine resins, melamine resins, benzoguanamine resins, cyanamide resins, aniline resins, water-dilutable or water-dispersible melamine or urea - Formaldehyde condensation products suitable.
  • amino crosslinker resins are used.
  • crosslinking agents may also be blocked polyisocyanates, for example based on 1,6-hexamethylene diisocyanate, bis (4-isocyanatocyclohexane) methane, 1,3-diisocyanatobenzene, tetramethylene diisocyanate, methyl pentamethylene diisocyanate, dodecamethylene diisocyanate, 1,4-diisocyanato-cyclohexane, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane, 4,4'-diisocyanato-dicyclohexylmethane, 4,4'-diisocyanato-dicyclohexylpropane (2,2), 1,4-diisocyanato isocyanatobenzene, 1-methyl-2,4 (2,6) -diisocyanatocyclohexane, 2,4-diisocyanatotoluene,
  • polyisocyanates in polyurethane chemistry known per se higher functional polyisocyanates with uretdione groups and / or carbodiimide and / or allophanate and / or isocyanurate and / or urethane groups and / or iminooxadiazinedione groups and / or oxadiazinetrione groups and / or Use biuret groups as blocked crosslinking agents. It is also possible to use mixtures of different diisocyanates and / or polyisocyanates.
  • Suitable blocking agents for the aforementioned polyisocyanates may include monoalcohols, e.g. Methanol, ethanol, butanol, hexanol, benzyl alcohol, oximes, e.g. Acetoxime, methyl ethyl ketoxime, lactams, e.g. Caprolactam, phenols, CH-acidic compounds such as e.g. Acetoacetic ester or malonic acid ester, e.g. Diethyl malonate, dimethylpyrazole, amines such as e.g. tert-butylbenzylamine, triazole, dimethyltriazole, dicyclohexylamine or diisopropylamine.
  • monoalcohols e.g. Methanol, ethanol, butanol, hexanol, benzyl alcohol, oximes, e.g. Acetoxime, methyl ethyl ketoxime, lactams,
  • auxiliaries and additives may be, for example, cobinders known to those skilled in the art, drying agents, fillers, cosolvents, colorants or effect pigments, leveling agents, thickeners or matting agents.
  • compounds which have reactive groups relative to the crosslinking agent can also be used as auxiliaries and additives.
  • the coating compositions according to the invention can be used very well to produce a coating on a substrate. Such use is therefore a further object of the invention.
  • An application of the coating composition according to the invention can take place by known methods, for example by spraying, brushing, flooding or by means of rollers or doctor blades on any substrates.
  • the high stability of the coating composition to shear forces through the inventive aqueous polyurethane-polyacrylate dispersion can take place by known methods, for example by spraying, brushing, flooding or by means of rollers or doctor blades on any substrates.
  • Suitable substrates are, for example, metal, wood, glass, stone, ceramic materials, concrete, plastics, composites, textiles, leather or paper, which may optionally be provided with conventional primers prior to coating.
  • Particularly preferred substrates are substrates which have a surface of metal and / or plastic, also in the form of films.
  • the respective drying conditions to be used can be adapted to the crosslinking agents used and, if appropriate, auxiliary agents and additives used.
  • a coating is obtained which is characterized by very good mechanical and optical properties. Furthermore, the coatings of the invention are characterized by a high hiding power. A coating obtainable by using the coating composition according to the invention is therefore a further subject of the invention.
  • another object of the invention is a composite of a coating according to the invention and a substrate having a surface made of metal and / or plastic.
  • NCO contents were determined volumetrically in accordance with DIN-EN ISO 11909, unless expressly stated otherwise.
  • the mean particle sizes were determined by means of laser correlation spectroscopy (LKS) using a Malvern Zetasizer 1000 spectrometer from Malvern Instruments Ltd., with given Z average values.
  • the number average molecular weight was determined by gel permeation chromatography (GPC) in tetrahydrofuran at 23 ° C.
  • GPC gel permeation chromatography
  • the procedure is according to DIN 55672-1: "Gel permeation chromatography, Part 1 - tetrahydrofuran as eluent” (SECurity GPC system from PSS Polymer Service, flow rate 1.0 ml / min, columns: 2xPSS SDV linear M, 8 ⁇ 300 mm, 5 ⁇ mol RID detector).
  • This polystyrene samples of known molecular weight are used for calibration.
  • the calculation of the number average molecular weight is software-based. Baseline points and evaluation limits are defined in accordance with DIN 55672 Part 1.
  • the binder mixture was poured over a cleaned glass plate which was stored vertically / slightly obliquely for 2 hours at room temperature. This was followed by a visual
  • the coating materials were applied to a glass plate and dried for 20 minutes at 140 ° C in a laboratory oven.
  • Pendulum damping The measurement of the pendulum damping was carried out according to DIN EN ISO 1522 on a glass plate and was determined by König.
  • Yellowing The yellowing was determined with a multi-angle spectrophotometer in reflection mode against a white tile. The measured values ⁇ b * were determined in accordance with DIN EN ISO 11664.
  • the base paint tests were carried out in the complete setup.
  • the sheet material was coated with a ⁇ -OEM hydrofiller prior to application of the clearcoat.
  • the filler was baked at 165 ° C for 20 minutes.
  • the basecoat was applied by means of a flow cup gun and flashed off at 80 ° C or pre-dried for 10 minutes. Subsequently, a 2K-PUR-OEM clearcoat was applied and baked at 140 ° C for 30 minutes.
  • Optics The optics were assessed visually. Edge creep describes the contraction of the lacquer at the edges of the substrate, flooding describes the poor alignment / orientation of effect pigments.
  • Flip-flop effect The flip-flop effect was determined using a multi-angle spectrophotometer in accordance with DIN 6175-2.
  • Opacity For the opacity, the basecoat was scrape on a black and white card and visually assessed.
  • Desmodur ® W 4,4'-diisocyanatodicyclohexylmethane, trans-trans content about 20 wt .-%, Bayer MaterialScience AG, Leverkusen, DE
  • Desmodur ® I l-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl cyclohexane, Bayer MaterialScience AG, Leverkusen, DE
  • MMA Methyl methacrylate
  • Tanemul 951 Emulsifier (Tanatex, DE) Butyl diglycol: 2- (2-butoxyethoxy) ethanol (BDGL): CAS 112-34-5, Colulater (Sigma-Aldrich, DE)
  • Byk 346 polyether-modified siloxane, additive for reducing surface tension to improve substrate wetting (Byk Chemie GmbH, DE)
  • Luwipal 073 melamine resin dissolved in water (BASF, DE)
  • DMEA ⁇ , ⁇ -dimethylethanolamine, neutralizing agent (Sigma-Aldrich, DE)
  • Butyl glycol 2-butoxyethanol (BG): CAS 111-76-2, Colinater (Sigma-Aldrich, DE)
  • Additol XL 250 wetting and dispersing additive (Allnex, BE)
  • a mixture of 308 g of Desmophen ® C 1200, 25 g of dimethylolpropionic acid, 10 g of neopentyl glycol, 1 g of butyl glycol and 161 g of acetone were heated to 55 ° C and stirred. Then 41 g Desmodur ® W and 93 g Desmodur ® I were added and heated to 65 ° C. At this temperature was stirred until an NCO content of 1.8% was reached. It was then cooled to 60 ° C and 12 g of dimethyl ethanolamine was added. 648 g of this solution were with vigorous stirring in 812 g of water, which was initially charged at a temperature of 35 ° C, dispersed.
  • Example 2 Preparation of the polyurethane urea dispersion as a precursor PUR 2 (Comparative)
  • a mixture of 202 g of Desmophen ® C 1200, 172 g of polyester polyol I, 29 g of dimethylolpropionic acid, 8 g of neopentyl glycol, 1 g of butyl glycol and 188 g of acetone were heated to 55 ° C and stirred. Then 46 g Desmodur ® W and 106 g Desmodur ® I were added and heated to 65 ° C. At this temperature was stirred until an NCO content of 1.7% was reached. It was then cooled to 60 ° C and 14 g of dimethyl ethanolamine was added.
  • Average particle size 69nm pH (10% Fh, 20 ° C): 7.8
  • a mixture of 344 g of polyesterpolyol I, 29 g of dimethylolpropionic acid, 8 g of neopentyl glycol, 1 g of butylglycol and 178 g of acetone were heated to 55.degree. C. and stirred. Then 46 g Desmodur ® W and 106 g Desmodur ® I were added and heated to 65 ° C. At this temperature was stirred until an NCO content of 1.8% was reached. It was then cooled to 60 ° C and 14 g of dimethyl ethanolamine was added. 600 g of this solution were dispersed with vigorous stirring in 751 g of water, which was initially charged at a temperature of 35 ° C. After dispersion was stirred for 5 min.
  • a mixture of 376 g of Desmophen ® C 1200, 29 g of neopentyl glycol, 1 g of butyl glycol and 190 g of acetone were heated to 55 ° C and stirred. Then, 50 g Desmodur ® W and 116 g Desmodur ® I were added and heated to 65 ° C. At this temperature was stirred until an NCO content of 2.7% was reached. The mixture was then cooled to 60 ° C and dissolved in 1122 g of acetone, and stirred for 5 min.
  • Viscosity (D 40 S 1 ): 1560 mPas General Preparation of the Polyurethane-Polyacrylate Dispersion (PUR-PAC 1-4)
  • reaction mixture was stirred for an additional hour at 75.degree. Finally, it was cooled to 25-30 ° C. and the batch was filtered through a 125 ⁇ m filter.
  • Tab.l formulations for the preparation of PUR-PAC dispersions PUR-PAC 1-4 (composition in wt .-% and characteristics of the respective dispersion).
  • reaction mixture was stirred for an additional hour at 75.degree. Finally, it was cooled to 25-30 ° C. and the batch was filtered through a 125 ⁇ m filter.
  • the dispersion PUR-PAC 8 can not be used as a varnish.
  • Table 3 Formulations for the preparation of PUR-PAC dispersions PUR-PAC 7 and 8 (composition in% by weight and characteristics of the particular dispersion).
  • Tab. 4 Formulations for the preparation of the infusion film (composition in grams).
  • test clearcoat For the preparation of the test clearcoat, the components were weighed in succession and stirred together. With a DMEA solution, 5%, the pH was adjusted to 8.0-8.5.
  • Tab. 5 Formulations for the preparation of the clearcoat film (composition in grams).
  • BYK 346 form of delivery 0.03 0.03 0.03 0.03 0.03 0.03 0.03 dist. Water 0,50 0,60 0,60 1,00
  • the PUR-PAC dispersion was initially charged and mixed with a mixture of dist. Water and butylglycol mixed. With a DMEA solution, 10%, the pH was adjusted to pH 8.0-8.5. The mixture was then stirred for 5 minutes at about 2000 rpm (5.2 m / s) under the dissolver. Then a mixture of Luwipal 073, butyl glycol and dist. Added water and stirred again for 5 minutes at about 2000 rev / min (5.2 m / s) under the dissolver. This was followed by the addition of the prepared metallic paste (Table 5), which was incorporated under the dissolver for 30 minutes at approximately 4000 rpm (10.5 m / s).
  • Tab. 6 Formulations for the preparation of the basecoat film (composition in grams).
  • the components were weighed in succession and premixed under a propeller stirrer.
  • the pH should be at pH 8.0-8.5 and, if necessary, adjusted with DMEA.
  • the paste was mixed at 10.5 m / sec under the propeller stirrer for 30 minutes, so that the temperature would not exceed 50 ° C as much as possible.
  • Tab. 7 Formulation for the preparation of the metallic paste (composition in grams).
  • the loop stability of the aqueous polyurethane-polyacrylate dispersions was simulated by means of a Göttfert capillary rheometer.
  • 500 g of the corresponding dispersion PU PAC 1 to PUR-PAC 4 were added to the container and pressed by means of a movable cylinder at a constant speed through an annular gap of 20 ⁇ gap size. If the material is shear-stable, it can be pushed through the annular gap without pressure build-up. With non-shear stable material, the dispersion coagulates, clogging the nozzle and pressure build-up is detected.
  • the shear forces simulated in this case can be calculated on the basis of the gap size and the speed and in the present case were 375,000 1 / s.
  • the results of the measurement of the loop stability are shown in Figure 1. From the graphs it can be seen that the shear stability could be significantly improved by the polyurethane-polyacrylate dispersion PUR-PAC 1 according to the invention, since the pressure only increased slightly, while the pressure on testing the dispersions prepared as comparative examples (PUR-PAC 2 to 4 ) increased significantly and increased to higher pressures.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Polyurethanes Or Polyureas (AREA)
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Abstract

L'invention concerne une dispersion aqueuse de polyuréthane - polyacrylate, pouvant être obtenue par polymérisation radicalaire d'un composant A). La dispersion aqueuse de polyuréthane - polyacrylate comprend un composé insaturé éthyléniquement, au moins en présence d'un composant B), comprenant de l'eau et une résine de polyuréthane, pouvant être obtenue en faisant réagir les composants structurels suivants I), comprenant au moins un composé aliphatique, cycloaliphatique, araliphatique et/ou aromatique, avec au moins deux groupes isocyanate ou plus, II), comprenant au moins un polyol de polycarbonate ayant un poids moléculaire moyen allant de 500 à 3000 g/mol, III), comprenant au moins un composé d'hydrophilisation anionique, qui présente au moins un groupe fonctionnel OH ou NH et qui contient un groupe carboxyle et/ou carboxylate, IV), comprenant au moins un polyol et/ou une polyamine ayant un poids moléculaire moyen situé entre ≥ 62 et ≤ 500 g/mol ainsi que, le cas échéant V), comprenant au moins un ou plusieurs monoalcools et/ou monoamines, un initiateur hydrophile étant mis en œuvre comme initiateur de la polymérisation radicalaire.
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